Composition of and method for the treatment of hydrocarbon compounds



Patented Jtlly 14, 1931 unnan STATES PATENT OFFICE WILLIAM E ELLIOTT, OFSTRUTHERS, OHIO, ASSIGNOI}. TO BY PR O MANUFACTURING COMPANY, 01EPITTSBURGH, PENNSYLVANIA, A CORPORATION OF DELAWARE COMPOSITION OF ANDMETHOD FOR THE TREATMENT OF HYDROCABBON COMPOUNDS I No Drawing.

This invention relates to material for and the method of treatinghydrocarbon compounds for the purpose of increasing the fuel valuethereof,.;and for recovering oil from waste hydrocarbon .materials, orfar]- in ci 'eas"ing. the fuel oil yield of various hydrocarboncompounds.

The invention s, especially, applicableto the treatment of fuel oil,bottom sediment, residuums from batch stills and heavy pressure stills,sludges, emulsions of petroleum, etroleum,, slop oils and varioushydrocarbon compounds which are at present con- =i lered to be largelywaste materials or from which fuel oil is at present only reization ofsuch fuel oil, and hence much difficulty is experienced in its use dueto the fact that these heavier hydrocarbon compounds cause carbondeposits on burner tips, furnace walls, grates, in stacks, and on boilertubes. Further trouble is experienced by reason of the tendency of.these heavienconn pounds to settle out in tank cars and In o1l lines.They tend to coagulate and obstruct strainers and meters, Iffuel oil isallowed to stand for any. considerable time, these heavy masses willform a semi-solid mass in the bottom of a tank. Furthermore, the watercontent of fuel oil,-.whichranges from 2% to 7%, utilizes a considerableportion of the heat energy of the oilwhen the oil is being burned,thereby lowering the flame tem-- perature and consuming some of theavailv present invention, itsvapor tension is de-' creased so that thereis less loss due to evap-' able heat of the oil.

The coa 'ulated mass, which forms in the bottoms of the .storagertanksis commonly referred to as bottom sediment. Heretofore most of thisbottom sediment has been waste Application filed July 28,

fuel

1927. Serial 1%. 209,187.

product. It has heretoforebeen an sive operation to recover any of theavailable fuel oil contained therein. The coagu lated particles whichform this bottom sedi-- ment distributed through the mass of fuel oilare not properly atomized in oil burners; and are the cause of thecarbon deposits,- as

hereinbeforepointed out. i

The hot residuums from high pressure stills contain considerable fueloil, but heretofore it has only been with considerable difliculty andexpense that the oil could be removed or these residuums be consumed bybeing mixed with other oil. Some of these residuums are solid orsemi-solid masses and are frequently referred to as coke or floatingcarbon, and to be consumed advantageously must-be mixed with heavy oiland after being mixed with oil, the mixture must be immediately burnedor the residuums will settle out. Various hydrocarbon refuse inv arefinery is emptied into sewers. These waste hydrocarbons are generallytermed slop oils. The available .fuel oil content in this slop oil hasheretofore been so diflicult to extract that the slop oils areconsidered a waste product. 1

By the process of the present invention, I treatthe hydrocarbonmaterials with a relatively small quantity of a material which, throughsome action, possibly catalytic in batch stills and" I its nature,functions as a dispersing medium, breaks up the emulsified formationsand deflocculates' the minute particles of the heavier hydrocarboncompounds, thereby bringing the 'oil into a homogeneous state andpreventing the further formation of emulsions therein. In breaking upthe emulsions the water and dirt, such as oil silt, is released and isfree to precipitate or rise to the top, dependingup'on the specific gravity of the hydrocarbon'material being treated. The oil treated orrecovered by the present process is permanently stable.

When fuel oil is treated according to the clean the oil lines,strainers, meters, and

burners of any coagulated formations and will keep them clean. Thistreatment of the oil, because it effects the removal of substantiallyall of the contained moisture,

leaves a dry, snappy fuel.

The material which I use for the treatment of the hydrocarbon com oundsconsists of naphthalene in a pow ered granular form, purified andtreated withrelativel small uantities of other substances whic have t eeifect of holding it in its granular form and preventing the naphthalenefrom becoming crystallized or otherwise deteriorating.

According to this invention, seventy ounds of naphthalene are groundinto powdered granular form and simultaneously subjected to thepurifying action of air. This may be done for instance, by allowing theowdered naphthalene tof'al through a co umn of air whereby 'it isbrought into intimate contact with the air. The powdered naphthalene isthenscreened, preferably in an eighteen to twenty-two mesh screen, afterwhich approximately one gallon of nitro-benzol or lemon colored oil of:mirbane are thoroughly mixed therewith for a period of about twentyminutes. Then approximately three pints of white medicinal parafiine, ormedicinal parafiine oil, and approximately two and one-half ounces ofoil soluble red aniline are added thereto and mixed therewith until thevarious substances are thoroughly commingled. After the mixture hasstood for approximately tWenty-four hours, it is ready for use in thetreatment of hydrocarbon compounds. It is desirable that the mixtureshould stand for at least twenty-four hours before it is used, but it isnot injured by standing longer. As a matter of fact, it is im roved bystanding, so that it can be stored indefinitely until such time as it isneeded in the treatment of hydrocarbon materials.

In the treatment of hydrocarbons, the naphthalene compound is added tothe hydrocarbon. .Generally speaking, approximately one pound of thenaphthalene compound is used for every eight hundred to one thousandgallons of hydrocarbon material at normal atmospheric temperatures. Thematerial is introduced into the hydrocarbon to be treated while thehydrocarbon is at normal temperatures and a-fter the introductionthereof, the hydrocarbon material may be heated to the desiredtemperature in order to facilitate the reaction. The reaction will takeplace in the hydrocarbon material at atmospheric temperature, butconsiderable more time is required,

, mixture can rea .some fuel oils and other h drocarbon substances meltsat F. w ile the asphalt content in some hydrocarbon materials melts at118 F. If the hydrocarbon material is heated sufiicientl to melt theasphalt or the arafline, t e naphthalene dily permeate the mass toeffect the desired reaction. At this temperature, however, thehydrocarbon material is not heated sufliciently to drive off the lighterhydrocarbons which are held in suspension.

The effect of the treatment is to break up all emulsified formations,separating the water from the hydrocarbon compounds. The heavyhydrocarbons in these emulsions are deflocculated upon the breakingdown.

of the emulsions and are held in suspension, thus producing a permanenthomogeneous body of oil. The water is precipitated to the bottom of thetreating tank while the homogeneous oil rises to the to In the treatmentof fuel 0i ractically. all of the moisture is precipitated andpractically all of the heavier emulsified hydrocarbons are broken up,whereby the fuel oil may be efiectively atomized and burned withoutproducing carbon deposits or smoke. In the treatment of tank sediment orbottom sediment, sludge or the like, water will accumulate at the bottomof the tank. The water as it accumulates should be drawn oil, for if itis allowed to remain in the treating tank, a strata of emulsion abovethe water and below the oil will remain. If the water is'drawn off thisstrata will be penetrated by the compound and under the mass action ofthe contents of the tank will be broken up throwing down additionalwater which in turn must be withdrawn. The separation of the oil fromthe water and the coagulated mass may be easily effected.

The treatment ofthe hydrocarbon materials may require several days, thelength of time depending on the nature of the material being treated andthe temperature at which the operation is carried out. Heating thehydrocarbon material accelerates the reaction, but the reaction willoccur more slowly at normal temperatures.

In reclaiming sludge or bottom sediment in storage tanks or othert heavysemi-solid masses of hydrocarbon, it is desirable to introduce oil Intothe mass prior to the introduction of the naphthalene compound. Onesatisfactory procedure is to first determine the number of gallons ofsludge in the tank to be treated and to then add two or more gallons ofoil for each gallon of sludge. One pound of the naphthalene compoundshould then be added for each eight hundred or one thousand gallons ofsludge and oil to be treated. After the introduction of the naphthalenecompound the sludge and stand for several hours or perhaps several days.At the end of this time, the moisture content may be withdrawn from thebottom of the tank while the oilwhich is recovered will rise to the topof the tank. It is, however, not necessary to mix the oil with thebottom sediment or sludge.

As a specific example of one application of the invention, theaccumulated sediment in a crude oil tank was treated in accordance withthis invention. tank were first heated to 180 F., at which time theoriginal gauge on the tank showed a depth of eleven feet nine inches.Two feet of water were drawn off after heating, leaving nine feet nineinches of stock in the tank. Samples were caught every two feet beforetreating with the following results:

Per cent Bottom sludge and water at 2' 98 Bottom sludge and water at 4Bottom sludge and water at 6 25 Bottom sludge and water at 8 20 Bottomsludge and water at 10' 2.4

The naphthalene content was thrown into the tank when the temperaturewas about 172 F. The tank was then closed and left to stand for fifteenhours, after which samples were taken every two feet with the followingresults:

I Per cent Bottom sludge and water at 2 80 Bottom sludge and water at 4'1 Bottom sludge and water at 6 2. 8 Bottom sludge and water at 8 1.2Bottom sludge and water at 10 1 After this analysis was taken additionalnaphthalene compound was introduced with the temperature of the tank atapproximately 188 F. After standing approximately twenty-four hours,further analysis was made with the following results:

Percent Bottom sludge and water at 2 1 Bottom sludge (no water) at 4 .2Bottom sludge (no water) at 6 .1 Bottom sludge (no water) at 8 .1

tank four feet from the bottom showed the oil to be both free of acidand alkali. The

content was less than 3%.

The contents of the v I "all types O'f'f'ue'loils and in the treatmentof various bottom sediments, and in the bottom two feet in the tank weredrawn ofi' and when the final sample was taken at two feet from thebottom, it showed 2.6% of bottom sludge.

From the foregoing it will be seen how a mass of sediment consistingverylargely of bottom sludge and water was reclaimed into oil where thetotal bottom sediment This indicates a reclamation of a very materialamount of oil which ordinarily could not be reclaimed, and'which, underpresent practice, would be mixed with fuel oil from'which it wouldeventually settle.

The above example is merely illustrative of'one application of theinvention. It has been successfully used in the treatment of treatmentof oil slop and sweetened cake and crude oils. The oil which has beentreated or recovered according to the present invention remainspermanently free of heavy sediment.

The invention has also been successful in the recovery of oil from tarwhich is obtained either as a coking plant by-product or from a gasproducer. The treatment of tar of this nature is substantially the sameas the treatment of fuel oil except that in the case of tar, the waterrises to the top of the tar since it is the lighter element.

. The invention may also be used in the treatment of various distillatesof petroleum, such as gasoline or kerosene. The effect of the treatment,either on fuel oil or other petroleum is to develop the maximum B. t.u.s and usually to lower the flash point.

Crude oil may be treated with the comppund to break up the heavyhydrocarbons and effect the separation of water and salt therefrom.Bottom sediments from crude oil storage tanks may be treated the same asbottom sediments from fuel oil tanks and made to yield a large quantityof oil. Various grades of crude oils, particularly the lower and heaviergrades can be advantageously treated.

When'crude oil is treated according to my process, water, or salt water,is precipitated.

and with the precipitation of the water, such foreign matter as silt anddirt are separated out of the oil. Crude oil may be treated to goodadvantage at normal temperatures and heating thereof is not necessary.

I have found that by grinding the naphthalene and then exposing thepowdered granular product to intimate contact with the air that morenearly uniform results are obtained than where the naphthalene is notbrought into contact with the air.

I claim:

1. A material for the treatment of petroleum distillates and otherhydrocarbons con sisting of naphthalene in-powdered granular form andhaving. relatively small quantities of lemon colored oil of mlrbane,paraffine oil and oil soluble red aniline mixed therewith. 3 Y

2. 'A composition for .the treatment of hydrocarbons comprisingnaphthalene, nitrobenzol, white parafiine oil and oil soluble redaniline.

3. A compound for the treatment of hydrocarbons comprising powderednaphthalene to which has been added lemon colored oil of mirbane in theproportion of one gallon of oil mirbane to approximately seventy poundsof naphthalene and having white parafiine oil and oil soluble redaniline mixed therewith.

4. A compound for the treatment of hydrocarbons comprising powderednaphthalene to which has been added lemon colored oil of mirbane in theproportion of one gallon of oil mirbane to approximately seventy poundsof naphthalene and having white parafline oil and oil soluble redaniline mixed therewith, the white paraffine oil being added in theproportion of approximately three pounds of oil to seventy pounds ofnaphthalene, and the oil soluble red aniline being substantially in theproportion of two and one-half ounces of aniline to seventy pounds ofnaphthalene.

5. A process for treating hydrocarbons which consists in adding to thehydrocarbon a relatively small amount of powdered naphthalene mixed withoil of mirbane, white parafiine oil and oil soluble red aniline.

6. A process for treating hydrocarbons which consists in adding to thehydrocarbon a relatively small amount of powdered naphthalene mixed withoil of mirbane, white parafline oil and oil soluble red aniline, heatingthe mixture and then. eflecting a separation of hydrocarbon oils andwater.

7. The method oftreating hydrocarbon material which consists in addingnaphthalene combined with oil of mirbane, parafli'ne oil and oil solublered aniline to the hydrocarbon, heating the hydrocarbon material, andseparating water therefrom.

8. The method of treating hydrocarbon materials which consists inpowdering naphthalene, mixing oil of mirbane, parafline oil and oilsoluble red aniline with naphthalene and introducing the naphthalene sotreated into the hydrocarbon material in the proportion of substantiallyone pound of naphthalene compound to each eight hundred to one thousandgallons of hydrocarbon material.

9. The method of treating hydrocarbon material which consists inpowdering and aerating naphthalene, mixing the powdered and aeratednaphthalene with lemon colored oil of mirbane, white parafiine oil andoil In testimony whereof I have hereunto set my hand. v

WILLIAM E. ELLIOTT.

